高分子金属微球的磁性能研究

在苯乙烯和丙烯酸共聚物「Ｐ（Ｓｔ－ｃｏ－ＡＡ）」，苯乙烯和４－乙烯吡啶共聚物「Ｐ（Ｓｔ－ｃｏ－４ＶＰ）Ｎｉ、Ｐ（Ｓｔ－ｃｏ－４ＶＰ）Ｃｏ金属微球，研究了它们的交流磁化率，磁滞回线，居里温度等磁性能。结果表明制得的了的微球为软磁材料，热重（ＴＧ）分析了则得Ｐ（Ｓｔ－ｃｏ－ＡＡ）Ｎｉ和Ｐ（Ｓｔ－ｃｏ－４ＶＰ）Ｎｉ的居时温度（Ｔｃ）分别为１７５℃和１８０℃，远远低于块状金属的居里温度值。     

聚硫堇修饰微带金电极的性质及对NADH的催化氧化

报道了硫堇在微带金电极上的电化学聚合过程，用红外光谱对聚硫堇进行了表征；研究了聚硫堇的电化学性质，发现聚硫堇在＋０．５～－０．７Ｖ（ｖｓ．ＳＣＥ）电位范围内有两对氧化还原峰，峰电位分别为：Ｅ＝－０．０３Ｖ、Ｅ＝０．０５Ｖ，Ｅ＝－０．２４Ｖ、Ｅ＝－０．１７Ｖ（ｖｓ．ＳＣＥ）。它们的式量电位Ｅ~（ｏ＇）随ｐＨ而变化，在弱酸性溶液中，Ｅ~（ｏ＇）／ｐＨ为－２９ｍＶ／ｐＨ（２５℃）；而在弱碱性溶液中则为－５６ｍＶ／ｐＨ。聚硫堇修饰微带金电极对ＮＡＤＨ的氧化具有催化作用，文中对电催化过程进行了探讨。     

大气有机物预浓缩用吸附剂富集特性的气相色谱法研究

用气相色谱方法研究了吸附剂对大气有机物的富集特性,提出用吸附参数泄漏体积ＢＴＶ（最大采样体积）以及脱附参数最低脱附温度或最小吹扫体积作为富集指标的新思想,并用冲洗色谱法测定了一些有机物在ＧＤＸ－３０１上的特性参数。不同温度的特性参数由１ｏｇ（ＢＴＶ）与１／Ｔｃ的线性关系外推得到。实验表明,所研究的２０种有机物（除了甲醇外）在装有２ｇＧＤＸ－３０１的采样管和０．１４ｇＧＤＸ－３０１的聚焦管上的最大采样体积分别不小于０．８Ｌ（３５℃）和０．３Ｌ（０℃）。     

修饰微带金电极上细胞色素C电极过程的热力学研究

研究了细胞色素Ｃ（Ｃｙｔ．Ｃ）在一种新的电子转移促进剂４，６－二甲基－２－巯基嘧啶修饰微带金电极（ＤＭＭＰ／Ａｕ）上的氧化还原热力学；求得Ｃｙｔ．Ｃ在ＤＭＭＰ／Ａｕ电极上反应的标准电极电位Ｅ＾ｏ，熵变△Ｓ＾ｏ，焓变△ＩＩ＾ｏ及Ｇｉｂｂｓ自由能的改变△Ｇ１０值分别为：０．２７２Ｖ（ｕｓ．ＮＨＥ），－１２３．７Ｊ．ｍｏｌ＾－＾１，－６３．１ｋＪ．ｍｏｌ．ｍｏｌ＾－＾１和－２６．２ｋＪ．ｍｏｌ＾－＾１（     

水杨醛缩7—氨基—8—羟基喹啉—5—磺酸催化荧光法测定痕量钒（V）

水杨醛缩－７－氨基－８－羟基喹啉－５－磺酸（简称Ｓ７Ｎ８Ｑ５Ｓ）在酸性介质中分解，产物呈现荧光，Ｖ（Ⅴ）对该反应具有催化作用，本文建立了催化荧光法测定痕量钒的新方法。体系在ＰＨ＝２的柠檬酸钠－盐酸缓冲溶液中，λｅｘ／λｅｍ＝３４２／４９９（ｎｍ）。测定Ｖ（Ⅴ）的最佳反应条件为０．０４％Ｓ７Ｎ８Ｑ５Ｓ５．０ｍＬ，５％ＫＢｒＯ３５．０ｍＬ，缓冲溶液５．０ｍＬ，９０℃加热５ｍｉｎ。Ｖ（Ⅴ）含量在１２．０     

双金属杂原子分子筛CrCoBEA的合成、波谱及催化性能研究

采用水热晶化法首次合成出ＢＥＡ结构含铬、钴，双金属杂原子分子筛ＣｒＣｏＢＥＡ，对晶化时间，晶化温度，成胶配比等合成条件进行了优化研究，采用ＸＲＤ，ＦＴＩＲ，ＵＶ－ＶｉｓＤＲＳ，ＥＳＲ及催化反应等方法测试其物相、波谱性质和催化性能，结果表明物质的量比为ＴＥＯＳ：０．０１７「Ｃｒ（ａｃａｃ）３」：０．０１７「Ｃｏ（ａｃａｃ）３」：（０．５８－０．６４）ＴＥＡＯＨ：０．０１Ａｌ（ＮＯ３）３：（１６－２０     

0-3型PZT/P[VDF(77)-TrFE(23)]铁电复合物的非线性介电系数

用自建的非线性介电测试装置测得了０ － ３ 型ＰＺＴ／Ｐ［ＶＤＦ（７７） － ＴｒＦＥ（２３）］ 铁电复合物厚片在不同场强和温度下的线性和非线性介电系数。对于ＰＺＴ 体积含量Φ＞ ０ ．３ 的复合物,介电系数ε１ 随测试场强的升高显著增大。在Φ＜ ０ ．１ 时,可用Ｍａｘｗｅｌｌ－ Ｇａｒｎｅｔｔ 方程拟合实验结果。Ｂｒｕｇｇｅｍａｎ 方程适合于低电场（ ＜ １ ＭＶ／ｍ ） 下复合物介电系数的预测。随着退极化场系数Ｌｚ 的改变,用Ｙａｍａｄａ 模型可拟合不同场强下复合物介电系数随Φ的变化关系。ε１ 的温度依赖性显示了明显的热滞后效应。Φ值增大导致升温过程的居里温度Ｔｃ 降低。Φ＜ ０ ．３ 时,三阶非线性介电系数ε３ 随测试场强的升高而减小,而Φ＞ ０ ．４ 试样的ε３ 在６ＭＶ／ｍ 场强下出现极小值。高Φ值的复合物具有较大的ε３ 。高ＰＺＴ 含量的复合物在相变区出现较大的ε３值。ε３ 温度谱同样显示了与ε１ 类似的表观热滞后现象。     

Schiff碱药物对产气杆菌代谢抑制的热力学研究

用微量热法测定产气杆菌在不同温度条件下受到Schiff碱药物抑制的热谱曲线, 根据其指数生长期的热谱信息, 确定它在不同温度条件下的生长速率常数和反应活化能, 找出了该细菌的最佳生长温度。同时借用化学反应中的过渡态理论, 得到一系列热力学参数, 对细菌在受到抑制时的生长代谢进行了热力学分析。     

两种CO(Ⅱ)希夫碱配合物的合成、表征和氧合反应热力学

本文合成了两种新的Ｃｏ（Ⅱ）希夫碱配合物，双（２，４－二羟基苯乙酮）乙二胺合钴（Ⅱ）（Ｃｏ（ＣＯＥＮ）和双（对香兰素）乙二胺－乙氧基－醋酸钴（Ⅱ）（Ｃｏ（ＶＡＥＮ））。通过元素分析、红外光谱、摩尔电导、热分析等测试手段研究了配合的性质，并确定了配合物的组成。用气体吸收测量装置配合物分别在ＤＭＦ、ｐｙ等不同溶剂中于不同温度下的饱和吸氧量，求得氧合反应的平衡常数及热学参数。同时讨论了溶剂和配体结构对配     

THE STUDY OF STRUCTURE AND DYNAMICS OF DINUCLEAR COMPLEXES ［Mo（VI）］_2－EDTA AND ［Mo（VI）］_2－EGTABY~1HNMR

ＴＨＥＳＴＵＤＹＯＦＳＴＲＵＣＴＵＲＥＡＮＤＤＹＮＡＭＩＣＳＯＦＤＩＮＵＣＬＥＡＲＣＯＭＰＬＥＸＥＳ［Ｍｏ（ＶＩ）］_２－ＥＤＴＡＡＮＤ［Ｍｏ（ＶＩ）］_２－ＥＧＴＡＢＹ~１ＨＮＭＲＲｕｉＦａｎｇＳＯＮＧ；ＦｅｉＬＩ；ＧｕａｎｇＭｉｎＬＩＵ；ＹｏｕＧａ?..     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.